Process for printing textile materials of natural or regenerated cellulose with reactive dyestuffs

ABSTRACT

PROCESS FOR PRINTING TEXTILE MATERIALS OF NATURAL OR REGENERATED CELLULOSE WITH REACTIVE DYESTUFFS BY PRINTING ON SAID TEXTILE MATERIALS A PRINTING PASTE CONTAINING A THICKENING AGENT, WATER AND EITHER AN ORGANIC DYESTUFF CONTAINING AT LEAST ONE OF THE KNOWN REACTIVE GROUPS, OR AN ORGANIC DYESTUFF CONTAINING AT LEAST ONE NUCLEOPHILIC GROUP, AND A COLOURLESS ORGANIC COMPOUND WHICH CONTAINS AT LEAST TWO REACTIVE GROUPS WHICH ARE CAPABLE OF REACTING BOTH WITH THE FIBRE AND WITH THE NUCLEOPHILIC GROUPS OF SAID DYESTUFF, THEN PADDING THE PRINT SO ABTAINED, AFTER DRYING, WITH AN AQUEOUS SALT-CONTAINING SOLUTION OF AN AGENT HAVING AN ALKALINE REACTION AND SUBSEQUENTLY DWELLING THE PLAITED FABRIC.

United States Patent F 50, Int. Cl. D06p 1/38, 3/66 US. Cl. 8-62 3 Claims ABSTRACT OF THE DISCLOSURE Process for printing textile materials of natural or regenerated cellulose with reactive dyestuffs by printing on said textile materials a printing paste containing a thickening agent, water and either an organic dyestutf containing at least one of the known reactive groups, or an organic dyestutf containing at least one nucleophilic group, and a colourless organic compound which contains at least two reactive groups which are capable of reacting both with the fibre and with the nucleophilic groups of said dyestulf, then padding the print so obtained, after drying, with an aqueous salt-containing solu tion of an agent having an alkaline reaction and subsequently dwelling the plaited fabric.

This application is a continuation of application Ser. No. 681,103, filed Nov. 7, 1967, and now abandoned.

Belgian patent specification No. 679,670 describes a printing process in which the reactive dyestuff is fixed fast onto textile material of natural or regenerated cellulose by applying the dyestuif to the textile material in the first step by means of a printing paste which contains water and a thickening agent and, after drying, padding the print in the second step with an aqueous solution which contains an agent having an alkaline reaction, and subsequently exposing the printed fabric to air, i.e. exposing the treated and spread out material to the action of air before plaiting it. Generally, the minimum period for exposing the print to air is between 1 and minutes. The print thus obtained is then rinsed with cold Water and treated with hot water, subsequently soaped, rinsed again and finally dried.

According to the afore-named process reactive dyestulfs having a lower reactivity cannot be applied because a prolonged exposure to air corresponding to a prolonged fixing period of these dyestulfs cannot be realized on an industrial scale.

The present invention is based on the observation that reactive dyestuffs may be fixed fast onto textile materials of natural or regenerated cellulose by printing on the textile material either an organic dyestufif which contains at least one fi-hydroxyethylsulphone sulphuric acid ester group, a vinylsulphone group, a monochlorotriazine group, a dichlorotriazine group, a 2,2,3,3-tetrafluorocyclobutane-l-acryloylamino group, a vinyl-sulphonylamino group, a fi-phenylsulphonylpropionylamino group or a dichloroquiooxaline radical, or an organic dyestuif containing at least one nucleophilic group and a colourless organic compound which contains at least two reactive groups which are capable of reacting with the fibre and with the nucleophilic groups of said dyestuff, by means of a printing paste which further contains water and a thickening agent, then padding the print so obtained, after "ice drying, with an aqueous salt-containing solution of an agent having an alkaline reaction and subsequently dwelling the plaited fabric at about room temperature, for example, in the range of from 10 to 30 C. If required the padded print is exposed to air for a very short time, for example 5 to 30 seconds, before plaiting and dwelling it.

In comparison with the known process described in Belgian Pat. No. 679,670, the fixing process according to the present invention allows the use of reactive dyestuffs having a lower reactivity.

Moreover, in comparison with said hitherto applied printing process, the present invention possesses the advantage that reactive dyestuffs having a high reactivity with the fibre-in spite of the high content of alkalies in the padding solution and the long dwelling time, in some cases lasting for several hourscan be fixed without a reduction of the colour yield .by a re-saponification of the binding dyestuff-fibre occurring.

During the dwelling the printed textile material can be piled up on each other; staining does not occur.

As reactive dyestuffs there may be used according to the process of the present invention dyestuffs from different organic dyestutf classes, for example, azo dyestuifs and anthraquinone dyestulfs which contain at least one of the known reactive groups mentioned above or dyestuffs of such kind which-owing to the presence of nucleophilic groupsare capable of reacting with a colorless compound which contains at least two reactive groups, said groups being capable of reacting both with the fibre and with the nucleophilic groups in said dyestulfs.

As compounds containing at least two reactive groups which are capable of reacting with the fibre and with dyestufis containing nucleophilic groups there may be used, for example:

(a) 1,3,5-tri-(acryloyl)-hexahydro s triazine of the formula (b) Methylene-bisacrylic acid amide of the formula NHCO-CH=CH2 a NHCOCH=CH2 (c) 2,4,6-triethyleneimino-s-triazine of the formula As dyestuffs capable of reacting with colourless compounds Which contain at least two reactive groups there are preferably used azo dyestuffs and anthraquinone dyestuffs which contain as nucleophilic groups for example, sulphonic acid amide groups, N-monosubstituted sulphonic acid amide groups, hydroxy groups, mercapto groups and/or acetoacetyl groups and/or heterocyclic ring systems containing imino groups.

As the agent having an alkaline reaction an alkali metal hydroxide is preferably used. The period during which the print in its open width is exposed to air depends 3 on the concentration of the agent having an alkaline reaction to such an extent that the required period of contact of the printed material with the air is reduced with increasing concentration of alkali. If, for example,

product of oleic acid and N-methyl taurine) and finally rinsed and dried.

A yellow print was obtained having a good fastness to light and wet processing.

100 cc. of sodium hydroxide solution (38 Be.) are used 5 per litre of padding solution, the required minimum pe- EXAMPLE 2 riod for exposing the print to air is about seconds. The 40 parts of the dyestulf described in Example 1 were minimum period for dwelling the plaited print generally mixed according to the method of the said example to amounts to between 1 minute and 3 hours. For fixation form a printing paste. This printing paste was printed of the dyestuifs it is, however, possible to subject the 10 on a cotton fabric by means of a roller printing machine. printed goods for a substantially longer period to dwelling, After drying, the printed fabric was padded with a soluin some cases for example up to hours, without a tiou consisting of 100 parts by volume of sodium hydroxreduction of the colour yield occurring in the presence ide solution (38 B.), 150 parts of sodium carbonate, of the alkalies. 180 parts of sodium chloride, 50 parts of potassium car- In general, it is preferable to adjust the concentration 15 bonate, and made up to 1000 parts by volume with water, of the alkali in the padding solution in such a Way that and then exposed to air for 8 seconds. The plaited fabric the pH value is in the range of from about 13 to 14. The was then allowed to dwell for 15 hours at 15 C. optimum concentration of alkali and the period of con- After finishing the fabric as described in Example 1, a tact of the printed material in the air must be regulated yellow print was obtained, having a good fastness to in each case according to the reactive dyestuff used, or light and wet processing. according to the colourless compound containing at least EXAMPLE 3 two reactive groups.

Suitable thickening agents are neutral thickening agents 40 parts of the dyestuff of the formula or thickeners having a weakly alkaline reaction, for example, alginates, difierent types of gum, or alkyl celluloses or hydroxyethyl celluloses.

The present invention enables the fixation also of re- "F active dyestuffs showing lower reactivity which, accord- Ill 00 ing to the process disclosed in Belgian Pat. No. 679,670, cannot be applied. Moreover, in comparison with this l hitherto practised fixation method the present invention soiNa' represents the technical advance in that, when reactive dyestutfs are used, which can be applied according to the known process, the air treatment is considerably reduced or can be completely omitted. Q, Q H, m,

The following examples illustrate the invention, the parts being by weight unless otherwise Stated; were mixed with 50 parts of urea, dissolved in 300 parts EXAMPLE 1 of hot water and introduced into 400 parts of an aqueous methylhydroxyethyl-cellulose of 4%. 40 parts of the dyestufi of the formula 40 After the addition of 15 parts of the sodium salt of -NHC0-N=NUCO0Na naoas-o-mc-nzo-oze Ho- N SOzNB were mixed with parts of urea, dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% which contained 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener.

After the addition of 15 parts of the sodium salt of metanitrobenzene sulphonic acid, the whole was made up to 1000 parts by the addition of 195 parts of water.

The printing paste, prepared in such a Way, was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then the plaited fabric is dwelled for 5 seconds at 20 C.

The print thus obtained was then rinsed for about 10 minutes with cold water, treated for 3 minutes with hot water which contained 3 parts of a complex forming agent on the base of a polymeric sodium meta-phosphate per 1000 parts by volume, subsequently soaped for about 10 minutes with an aqueous solution of 1% strength of a synthetic detergent (sodium salt of the condensation metanitrobenzenesulphonic acid the whole was made up to 1000 parts by the addition of 195 parts of water.

The printing paste prepared in such a way Was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of parts by volume of sodium hydroxide solution (38 Be), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to air for 10 seconds. The plaited fabric was then allowed to dwell for 10 minutes at 20 C.

After finishing the fabric as described in Example 1, a yellow print was obtained, having good fastness to light and wet processing.

EXAMPLE 4 40 parts of the dyestuif described in Example 3 were mixed according to the method of said example to form a printing paste. This printing paste was printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 30 parts by volume of sodium hydroxide solution (38 Be), 150 parts of sodium carbonate, 180

parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for 10 seconds. The plaited fabric was then allowed to dwell for 45 minutes at 18 C.

After finishing the fabric as described in Example 3, a yellow print was obtained, having a good fastness to light and wet processing.

EXAMPLE 40 parts of the dyestufi described in Example 3 were mixed according to the method of said example to form a printing paste. This printing paste was printed on a staple fibre fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 30 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to an air passage for seconds. The plaited fabric was then stored for 45 minutes at 18 C.

After finishing the fabric as described in Example 3, a yellow print was obtained having a good fastness to light and wet processing.

EXAMPLE 6 40 parts of the dyestutf of the formula 0 H med a-r 1 were mixed with 50 parts of urea, dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous hydroxy-ethyl-cellulose of 4%. After the addition of 10 parts of the sodium salt of meta-nitrobenzene sulphonic acid the whole was made up to 1000 parts by the addition of 200 parts of water. The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to air for seconds. The plaited fabric was then allowed to dwell for 80 minutes at C.

After finishing the fabric as described in Example 1, an orange print was obtained, having a good fastness to light and wet processing.

EXAMPLE 7 40 parts of the dyestufi of the formula S O Na were mixed with 50 parts of urea, dissolved in 1300 parts of hot Water and introduced into 400 parts of aqueous alginate thickener of 4% which contained 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener.

After the addition of 15 parts of the sodium salt of meta-nitrobenzene sulphonic acid, the whole was made up to 1000 parts by the addition of 195 parts of water. The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate, and made up to 1000 parts by volume with water and then exposed to air for 20 seconds. The plaited fabric was then allowed to dwell for 2 hours at 20 C.

After finishing the fabric as described in Example 1, a blue print was obtained, having a good fastness to light and wet processing.

EXAMPLE 8 40 parts of the cobalt complex compound of the dyestufi of the formula NH, were mixed with 50 parts of urea, dissolved in 300 parts of hot water and introduced into 500 parts of an aqueous alginate thickener of 4%. After the addition of 10 parts of the sodium salt of meta-nitrobenzene sulphonic acid, the whole was made up to 1000 parts by the addition of parts of water.

The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodium hydroxide solution (38 B), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to air for 15 seconds. The plaited fabric was then stored for 3 hours at 25 C.

After finishing the fabric as described in Example 1, a black print was obtained, having a good fastness to light and Wet processing.

EXAMPLE 9 40 parts of a mixture of dyestuffs of the formulae Q- N N NaOzS S OaNa S OzNa wherein R stands for the grouping -s OPNHQ-S oi-om-om-o-soma benzene-sulphonic acid, the whole was made up to 1000 parts by the addition of 195 parts of water.

The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodium hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to air for 20 seconds. The plaited fabric was then allowed to dwell for 4 hours at 25 C.

After finishing the fabric as described in Example I, a turquoise blue print was obtained, having a good fastness to light and wet processing.

EXAMPLE 40 parts of a mixture of dyestuffs of the formulae Nfloss N= N l l N v m hu+lufl l N SOaNa NaO S N= =N N I N.... tu

I so N N 3 a NaO S wherein R stands for the grouping were mixed with 50 parts of urea, dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% which contained 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener. After the addition of parts of the sodium salt of meta-nitrobenzene sulphonic acid, the whole was made up to 1000 parts by the addition of 195 parts of water.

The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodiurn hydroxide solution (38 B.), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to air for seconds. The plaited fabric was then stored for 4 hours at 23 C.

After finishing the fabric as described in Example 1, a turquoise blue print was obtained, having a good fastness to light and wet processing.

8 EXAMPLE 11 40 parts of the dyestuif of the formula FCC F:

SO Na OH NH-oo-oH=oH-on-cm I N=N Na 038 LS O Na were mixed with 50 parts of urea, dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% which contained 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener.

After the addition of 15 parts of the sodium salt of meta-nitrobenzene-sulphonic acid, the whole was made up to 1000 parts by the addition of 195 parts of water.

The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of parts by volume of sodium hydroxide solution (38 Be), parts of sodium carbonate, parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to air for 15 seconds. The plaited fabric was then stored for 1 hour at 20 C.

After finishing the fabric as described in Example 1, a red print was obtained, having a good fastness to light and wet processing.

EXAMPLE 12 I moo-Gamer SOgNa were mixed with 100 parts of urea, dissolved in 200 parts of hotwater and introduced into 400 parts of an aqueous alginate thickener of 4% which contained 5 parts of a complex forming agent on the base of a polymeric sodium meta-phosphate per 1000 parts of thickener.

.After the addition of 15 parts of the sodium salt of metanitrobenzene sulphonic acid, the whole was made up to 1000 parts by the addition of 245 parts of water.

The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodium hydroxide solution (38 Be), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate and made up to 1000 parts by volume with water, and then exposed to air for 20 seconds. The plaited fabric was then stored for 2 hours at 23 C.

After finishing the fabric as described in Example 1, a scarlet print was obtained, having a good fastness to light and wet processing.

EXAMPLE 13 40 parts of the dyestuff of the formula some OH were mixed with 100 parts of urea, dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% which contained 5 parts of a 9 complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener.

After the addition of 15 parts of the sodium salt of metanitrobenzene sulphonic acid, the whole was made up to 1000 parts by the addition of 145 parts of water.

The printing paste prepared in such a way was then printed on a linen fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodium hydroxide solution (38 Be), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of ptassium carbonate and made up to 1000 parts by volume with water, and then exposed to air for 20 seconds. The plaited fabric was then stored for 10 minutes at 20 C.

After finishing the fabric as described in Example 1, an orange print was obtained, having a good fastness to light and wet processing.

EXAMPLE 14 40 parts of the dyestuff of the formula were mixed with 100 parts of urea, dissolved in 400 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% which contained 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener.

After the addition of 15 parts of the sodium salt of meta-nitrobenzene sulphonic acid, the whole was made up to 1000 parts by the addition of 45 parts of water.

The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodium hydroxide solution (38 B), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potassium carbonate, and made up to 1000 parts by volume with water and then exposed to air for 15 seconds. The plaited fabric is then allowed to dwell for minutes at 22 C.

After finishing the fabric as described in Example 1, a red print was obtained, having a good fastness to light and wet processing.

EXAMPLE 40 parts of the dyestuif of the formula were mixed with 50 parts of urea, dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% which contained 5 parts of a complex forming agent on the base of polymeric sodium meta-phosphate per 1000 parts of thickener.

After the addition of 15 parts of the sodium salt of meta-nitrobenzene sulphonic acid, the whole was made up to 1000 parts by the addition of 195 parts of water.

The printing paste prepared in such a way was then printed on a cotton fabric by means of a roller printing machine. After drying, the printed fabric was padded with a solution consisting of 100 parts by volume of sodium hydroxide solution (38 Be), 150 parts of sodium carbonate, 180 parts of sodium chloride, 50 parts of potas sium carbonate and made up to 1000 parts by volume 10 with water, and then exposed to air for 15 seconds. The plaited fabric was then allowed to dwell for 10 minutes at 20 C.

After finishing the fabric as described in Example 1, a red print was obtained, having a good fastness to light and wet processing.

What is claimed is:

1. A process for producing fast prints on textile materials of natural or regenerated cellulose fibers with reactive dyestuifs, which comprises printing on said textile materials a printing paste containing a neutral to weakly alkaline thickening agent, water and either an organic dyestulf containing at least one fi-hydroxyethylsulfonesulfuric acid ester group, vinylsulfone group, monochlorotriazine group, dichlorotriazine group, 2,2,3,3,-tetrafiuor0cyclobutane-l-acryloylamino group, vinylsulfonylamino group, fi-phenyl sulfonylpropionylamino group or dichloroquinoxaline radical, or an organic dyestufi containing at least one nucleophilic group and a colourless organic compound having the formula (a) 1,3,5-tri-(acryloyl)-hexahydro-s-triazine of the formula H2(|}/ \CH2 CHFCHCON 1 ICOCH=CH2 0 H2 (b) methylene-bisacrylic acid amide of the formula NHCOCH=CH2 NHCO-OHCH2 (c) 2,4,6-triethyleneimino-s-triazine of the formula H2C\ /N\ /CH2 the reactive groups of them being capable of reacting with the fibre and with the nucleophilic groups of said dyestutf, then padding the print so obtained, after drying, with an aqueous salt-containing solution of an alkali metal hydroxide and subsequently dwelling the fabric at temperatures ranging from 10 to 30 C.

2. A process as claimed in claim 1, wherein the concentration of the alkali in the padding solution is such that the pH value is in the range of from 13 to 14.

3. A process as claimed in claim 1, wherein the minimum time of dwelling the print is 10 minutes.

References Cited UNITED STATES PATENTS 3,043,650 7/1962 Wegmann et al. 854.2 3,044,843 7/ 1962 Tullio 817 3,084,017 4/ 1963 Reeves et al 854.2 3,334,961 8/1967 Kuhme et al 854.2 3,379,715 4/1968 Chiddix et al 8163 X FOREIGN PATENTS 679,670 10/ 1966 Belgium 854.2

GEORGE F. LESMES, Primary Examiner T. J. HERBERT, JR., Assistant Examiner US. Cl. X.R. 81 A 

